Osmotic priming reduces the longevity of Vigna radiata (mung bean) seeds during subsequent dry storage. The present study has investigated the relationship between volumetric changes, modified water sorption properties and the decrease in seed longevity after priming. Volumetric analysis of control embryos revealed two major dehydration-related volumetric contractions in the biopolymer matrix, reflecting structural reorganization in biopolymer matrix during drying. These contractions occurred at hydration from 0.29 to 0.23 g g-1 dw and from 0.18 to 0.11 g g-1 dw, respectively. Volumetric contractions were reduced significantly after priming and also occurred at higher water contents (i.e. 0.48-0.32 g g-1 dw and 0.21-0.11 g g-1 dw). Consequently, at the same water content, primed seed embryos had higher specific biopolymer volume and lower specific density than control embryos. Water sorption study showed that priming did not change the monolayer hydration value, but altered the properties of multilayer water sorption in seed axes. The analysis of water clustering function suggested that priming enhanced the water-water association in seed axes, but not in cotyledon tissues. Solid-state 1H-NMR (nuclear magnetic resonance) investigation confirmed that priming did not cause a significant change of water dynamic properties in cotyledon tissues at water contents below 0.20 g g-1 dw. The relevance of volumetric modifications of the biopolymer matrix and changes in water clustering function to the reduced seed longevity after priming is discussed. It is proposed that priming-induced increases in surface reactivity may enhance deteriorative chemical reactions in re-dried seed tissues.